Process for clarification of hydrocarbons containing suspended or colloidal complexes



\ No lJrawing.

cw Y Patented Sept. 20, 1932 UNETE STATE.

STEPHEN SWARTZ, OF LONG BEACH, CALIFORNIA, ASSIGNOR TO JENKINSPETROLE'O'lVI EROCESS COMBANY, OF CHICAGO, ILLINOIS, A CORPORATION OFWISCONSIN PROCESS FOR CLARIIICATION F HYDROCARIBONS CONTAININGISUSIPENDED OR,

/. COLLOIDAL This invention relates to certain improvements in theclarification of hydrocarbons in general and particularly to a processfor discharge of suspended or colloidal complexes 'and their removalfrom petroleum hydrocarbon intermediates and residuals.

In the liquid residuum from the dry distillation of crude hydrocarbonsand particularly as obtained from the cracking ofpetroleum hydrocarbons,there is usually produced among other impurities a varying colloidalcontent of tree carbon and semi-solid asphalt-i0 complexes of highmolecular weight, alike detrimental to the continuity of 3 the processand the quality of the residuum produced. Such objectionable results ofcolloidal formation have been completely overcome in the development ofa cracking process well known in the art, by the employment of finelydivided hydrate of lime as an adsorbent, in intimate contact with thepetroleum hydrocarbon undergoing cracking, such process being thesubject of a copending application. The fuel like residue continuouslyproduced by such process commonly carries in initial suspension apartially coagulated complex of hydrate of lime, in which variouscolloidal impurities incident to cracking, such as free carbon,asphaltic bodies of high molecular weight, etc., are

adsorbed; such complex usually settling in a zone of repose andproducing a supernatant fuel oil of acceptable marketable spec1fication.

Where however the cracking of heavy crudes or residuals is practiced bysuch pre-' viously mentioned process, or Where the final residuiunproduced approaches 1n specific gravity the limiting specific gravity ofthe -lime complex which becomes specifically llme component adsorbslighter as its increased quantlties of colloidal decomposition productsand enveloping medium q (a condition especially obtaining when crackingthe previously mentioned heavy crudes or residual petroleum hydrocarbonsin the presence of an excess of hydrate of lime) ;'such complex remainsin the final residuum continuously withdrawn from the system, renderingsuch residuum unsalable COMPLEXES Application filed February 2, 1929.Serial No. 337,167.

under the usual marketable requirements for admissible insoluble matter.1

Various methods have been proposed for the breaking down and removalofsuch suspended or colloidal complexes together with their resultantcoagulates, with attainment of the enveloping hydrocarbon medium in astate of clarification as the chief objective. For example: treatmentwith sulphuric acid. followed by settlingycentrifuging at hightemperatures; and filtration through diatomaceous earth have beenemployed with varying success; but all such methods have fallen short ofthe optimum, especially where considerable quantities of hydrate of limeare present; often involving either loss of desirable material,excessive amounts ofcorrectlve employed, production'of undesirable gummyacid complexes, and/or emulsions or elly like pastes that quickly clogthe instrumentalities involved. I Y

A specific object of the invention is to efiect the clarification of aliquid petroleum hydrocarbon containing a suspended colloidal complex,of which hydrate of lime is a component part, by discharging thecolloidal condition of such complex and removing the resultant coagulatefrom such liquid petroleum hydrocarbon, without appreciable loss ordetrimental action to the latter product.

An incidental object to the invention is to effect the clarification ofa liquid hydrocarbon containing a colloidal and/or semi-colloidalcomplex, by discharging the suspended colloidal condition of suchcomplex and removing the resultant coagulate from such liq uidhydrocarbon, without appreciable loss or; detrimental action to theoriginal components of the colloidal complex or coagulate pro-v duced. 1

To attain such previous described objectives, an important generalpreliminary purpose of the invention is to inhibit the-ionization ofsuchcomponent of acolloidal complex of which an. adsorbent having theeffect ot-hydrate of lime is a part existing in a liquid hydrocarbonmedium, by the introduc ions to the point of colloidal discharge;without such introduced electrolyte itself undergoing substantialionization.

A specific preliminary object of the invenl tion, where a colloidalcomplexexistingin a liquid hydrocarbon medium contains free hydrate oflime, is to introduce to such colloidal zone a corrective electrolyte,of such composi- V tiona's to change the pH concentration to thepotential ionic difierence necessary to discharge of such existingcolloidal condition;

without such introduced electrolyte itself undergoing substantialionization.

A further preliminary purpose of the invention, corollary to the twoimmediately preceding objectives, is the employment of the correctiveelectrolytefin a solution inhibitive of substantial ionization, and inaddition'to the conditions alreadyimposed,.such electrolyte should bepreferably soluble in a petroleum hydrocarbon liquid over a wide rangeof temperatures.

An important ob ect of the. invention is to effect the introduction ofsaid corrective electrolyte to the colloidal zone in such quan-;

tity, state of concentration and manner, as

to secure a surface and/or filmf reaction between the electric ioniccharges involved, rather than efiecting any substantial molec ularchemical transformation in the complex to be discharged. r

. An equally important related object of the invention is to securesuchfilm reaction and reduction of potential difiference in the colloi dalsystem as may be necessary to effect its discharge, by the introductionof said corrective electrolyte as an adsorbed film in a substantiallyneutral finely divided adsorptive media, such as diatomaceous earth,fullers earth and the like; to thoroughly incorporate such'adsorbentv(pretreated to the point of saturation) with the colloidal mixture tobe clarified, and to finally separate the resultant coagulate produced,fromits enveloping liquid medium, through the agency of a centrifuge,filter," filter press'and/orother in strumentality well known in theart.

- An additional object of the invention, res

s'embling the preceding, but of less efficient degree per unit of'material employed, in-.

' its enveloping hydrocarbon medium, at temperatures respectively bestsuited for such discharge and removal of'such coagulate;

with due regard to the viscosity and other physical characteristics ofthe hydrocarbon medium involved. I

A final general object of the invention is to'effect the separation-ofthe discharged colloidal'complex from its liquid hydrocarbon medium,under aforce best suited to produce amammum economic yieldof requiredspecification, clarified hydrocarbon, and a mini- I mum quantityof'substantiallydry rej ect'; and

whilev such force of separation may be developed centrifugally, I obtainexcellent results with afilter press of a type well known in) the art,although continuous filtration,

under any desired absolute pressure may be also employed toadvantage. I

While in general, only limiting myself to a type of correctiveelectrolyte within the speci: fications thus far imposed (the termelectrolyte being held to mean'a'single or mix ture of electrolytes), Iprefer to employ for such purpose,'where hydrate of limeis a componentof the colloidal complex to be discharged, 7 such naphthenic and/orsulfonaphthenic acids as are obtainable from the wastelyes of petroleumrefining; such acids on account of theirsolubility in a petroleumsolvent, and low ionization therein, proving ideal for securing thenecessary pH concentration for colloidal correction; To secure optimumeconomic results from such naplr thenic and/or sulfonapht-henic acids, Idissolve them in a petroleum solvent of low commercial value, such asgasoil, for example; employing such solution in a low state of acidconcentration in quantity sutficient to saturate the adsorptive or inertcarrier selected. I then incorporate such pretreated saturatedadsorptive or inert absorbent carrier with the hydrocarbon containingthe colloidal complex to be vdischarged, transfer the resultant mixtureof hydrocarbon and coagulate to ;a filter press; andsubsequently recoverthe hydrocarbon medium as a clarified, specification product, and theformer colloidal complex'as an essentially dry, non-colloidal,permeable,

easily separable cake from the press, containingin addition to theoriginal constitu;

ents of the complex, the added adsorptive and electrolytewithsuch addedadsorptive imparting a self-filtering value to the cake, and admittingto a marked degree of a thickness of formation, dependent upon thestrength of the supporting cloth and/or screen, rather tha'n'frompressure developed impedance of'flow. Equally good results may beobtained by substituting'the naphthenic acids obtained from-waste lyeswith petroleum and/ or naphthenicand sulfonaphthenic acids obtaining inthe socalled acid oil, separable from sulphuricacid sludge; in whichcase the acid oil, properly diluted to the desired degree with anadditional quantity of petroleum solvent may be employed direct tosaturate the selected adsorptive; the steps of theprocess beingotherwise identical.

The temperature at which incorporation of the pretreated a-dsorptivewith the hydrocarbon to be clarified occurs, as well as the generalcomposition of the latter, also has an eiie'ct on the colloidaldischarge reaction, and

' a preliminary laboratory test best determines the proper quantities ofthe discharge agents to be employed for any clarification problem; butin general too great a concentration of electrolyte, excess ofadsorptive, or operation at too elevated a temperature will producegummy reaction products, greatly hindering ties of discharge agents aredlsclosed, but

the subsequent removal of the coagulate formed and the production of amaximum yield of clarified hydrocarbon.

in order that the invention may be better 7 understood, reference willbe made to a typical clarification problem, where the quantias allreactions may be conducted in apparatus well known to those skilled inthe art of refining, no drawing accompanies the specification.

Thus, the clarification of an 8A. P. I. gravity petroleum residuumproduct from a cracking plant, containing a semi-colloidal complex of 16pounds to the 42 U. S. gallon barrel, of which 10-12 pounds are calciumcompounds, with'hydrate oflime in excess, will be considered. In suchinstance, optimum results have been secured by incorporating with suchproduct at 350 F., in an ordinary jacketed mixer, fitted with the usualmechan ical stirring device, aqua-ntity'of pretreated diatomaceousearth, screening approximately over 200 mesh to the inch, on the basisof one half pound of pretreated earth to the barrel of residuum to beclarified and then transferring the mixture of residuum and coagu lateproduced to a filter press, building up a filtering pressure ofapproximately 100 pounds. For pretreatment of the diatoma- 'ceous earth,gas oil, containing naphthenic and "sulfona-phthenic acids at aconcentration of N/ 10 is employed, in volume sufficient" to thoroughlysaturate the earth. and to :11 low pumping of the treated material; thefinal results of such operation being a clarifiedpetroleumresiduum,containing less than 0.25% insoluble mineral matter; and ancssentiallydry, permeable cake in the filter press, easily detachable therefrom,and without gummy or sticky qualities;

It will be understood the process is not lim-, ited to the exactquantities, concentrations,

temperatures and pressures disclosed in the preceding paragraphs, nor toany specific discharge agent previously described. Neither is theprocess restricted to any particular apparatus or instrumentalitv thathasbeen mentioned as incidental to securing the desired objectives,nor-need the exact order of process procedure thus far discussed be em--ployed;; as for example the process may be operated inlbatch,intermittently with such short intervals between phases asto beessentially continuous, or absolutely continuous according to the sourceoisupply, which if;

at an elevated temperature may furnish any operative heat required; andwhat Iclaim is new, and" desire to protect by Letters Patent is: y

1. A process of clarifying petroleum hydrocarbon oil containingsuspended or colloidal complexes of hydrated lime and associatedcarbonwhich comprises dissolving an organic acid containing a naphthenering, such as naphthenic acid, in a petroleum solvent, such as gas oil;saturating a finelydivided solid mineral adsorbent with such solution ofsaid acid'in said solvent; and introducing said adsorbent so treatedinto the petroleum 11ydrocarbon oil, whereby said suspended or colloidalcomplexes are contacted withsaid acid and coagulated.

2. A process of clarifying petroleum hydrocarbon oil containingsuspendedor 001-. loidal complexes of hydrated lime and .asso ciated carbon whichcomprises dissolving an organic acid containing a naphthene ring,

vent, such as gas oil; saturating a finely divided solid absorbent withsuch solution or" said acid in said solvent; and introducing saidmineral absorbent so treated into the petro leum hydrocarbon oil,wherebysaid suspended or colloidal complexes are contacted with saidelectrolyte and coagulated.

3. A process of clarifying petroleum hysuch as naphthenic acid, in apetroleum sol- I drocarbon oil. containing suspended or colleum acid,containing a naphthene ring, de-

rived from the waste lyes of petroleum refining in a petroleumdistillate,'such as gas oil; saturating a finely divided mineraladsorbent, such as fullers earth or diatomaceous earth, with suchsolution of said acid in said gas oil; and introducing said adsorbent sotreated into the petroleum hydrocarbon oil whereby said suspended orcolloidal com plexes are contacted with said acid'and coagulated.

5. A'process of clarifying petroleum hydrocarbon oil containingsuspended or colloidal complexes of hydrated lime and associated carbonwhich comprises'efiectinga mixture of a petroleum acid, containing anaphthene .ring, derived from the waste oil separable from the sulphuricacid sludge ofpetroleum refining with a petroleum distillate, such asgas oil; saturating'a finely divided mineral adsorbent, such as fullersearth or diatomaceous earth, with such mixture; and introducing saidadsorbent so treated into the petro-' leumhydrocarbon oil, wherebysaid'suspenddxor colloidal complexes are contacted with said mixture andcoagulated.

6.1m the treatment of petroleum 'hydro carbon oil which has beensubjected to a a cracking reaction, wherein said oil contains suspendedor colloidal hydrated lime associated with carbon and carbon formingsubstance, the process which comprises introducing into such oil apetroleum acid containing anaphthene ring dissolved in a petroleumdistillate, such as gas oil; saturating a finely divided, solid mineraladsorbent such as fullers earth or diatomaceous earth with said solutionof said acid in said distillate; intro ducing said adsorbent so treatedintothe petroleum hydrocarbon oil, whereby said suspened or colloidalcomplex is contacted with said acid and coagulated; and removing saidcoagulated complex from the remaining liquid petroleum hydrocarbon oilby filtration. I r

7 A process of clarifying petroleum hydrocarbon oil containing.suspended or colloidalcomplexes of hydrated lime and associated carbonwhich comprises dissolving a petroleum acid derived from'the waste .lyesof petroleum refining and substantially insoluble in water in apetroleum distillate, saturating a finely divided mineral adsorbent withsuch solution of said acid'in said distillate; introducing saidadsorbent so saturated into the petroleum hydrocarbon oil, intimatelycontact ng said suspended or colloidal com-. plexes with the acidsaturated adsorbent whereby the former are coagulated, and removing thecoagulated complexes othydra't'ed lime and associated carbon from thepetroleum hydrocarbon oil.

8. Aprocess of clarifyingpetroleum hydrocarbon oil containing suspendedor colloidal complexes of hydrated'lime and associated carbon whichcomprises diluting waste of petroleum refining and substantially in.-

oil separable from the sulphuric acid sludge soluble in water with apetroleum distillate inhibitive of substantia ionization, saturating afinely dvided mineral adsorbent with such diluted waste oil';introducing said adsorbent so saturated into the petroleum hydrocarbonoil, intimately. contacting said suspended'or colloidal complexes withthe sat-- urated adsorbent whereby the former are 00- agulated,andoremoving the coagulated complexes of hydrated lime. and associatedcarbon from the petroleum hydrocarbon oil.

A process of clarityingpetroleum hydro carbon oil containing suspendedor colloidal complexes of-hydrated lime and assoclated carbon whichcomprises dissolving an organic electrolyte of acid reaction andsubstantially insolublein water in a solventinhibitive of substantialionization, saturating a finely divided mineral adsorbent with suchSOlHtlOn of said electrolyte; introducing said adsorbent so saturatedinto the petroleum hydrocarbonoil, intimately contacting said suspendedor colloidalcomplexes with thewsaturated adsorbent whereby the'formerare coagulated, and removing the 'coagulated complexes ofhydrated lime and associated carbon from: the petroleum hydrocarbon:oil.

10. Aprocess of clarifying petroleum hydrocarbon oil containingsuspended or colloidal complexes of hydrated limeand associated carbonwhich comprises dissolving a petroleum acid derived from the wastelyesof petroleum refining and substantially in soluble in water in gas oil,saturating a finely divided, mineral adsorbentfsuch asdiatomace'ous-earth, with such solution of said-acid insaid gas foil;introducing said adsorbent so saturated into the petroleum hydrocarbonoil,. intimately contacting said suspendedv or colloidal complexeswiththe acid saturated adsorbent whereby the colloidal condition of saidcomplexes is discharged and said com-V plexes are coagulated, andremoving the coagulated complexes, 'ofhydrated lime and associated[carbon from the petroleum carbon oil. v i v- 11. ,Aprocess ofclarifying petroleum hydrocarbonoil containing suspended or colloidalcomplexes of hydrated'lime and associated carbonewhich comprisesdissolving an organic electrolyte. of acidreac-tion and sub st'antiallyinsoluble in water in gas oil, satus rating a finely divided vmineral"adsorbent,

hydroe such as diatomaceous earth, with said elec-r tionable solidmaterials which comprises adding lime to hydrocarbon oil and subjectingsuch oil to cracking conditions to obtain vaporous products andunvaporized fueloll containing suspended or colloidal complexes. of limeand associated carbonaceous 1 mate. rial formed in the hydrocarbonoilundersaid crackingconditions, withdrawing said fuel oil from saidcracking conditions, saturating a finely divlded SOllCl mineraladsorbent, such as fullers earth or diatomaceous earth, with waste Ollseparable from the sulphuric acid sludge of petroleum refining,dispersing said adsorbent so treated throughout said fuel oil to efie'ctsuch coagulation of said suspended or colloidal complexes as to permitsettling thereof, settling the coagulated complexes of hydrated lime'andassociated carbonaceous material from said fuel 011, and drawmgofi thefuel 011 thus clarified and substantially free from carbon and otherobjectionable 7 intimately contacting said suspended or colloidalcomplexes of lime and associated carbonaceous material contained in saidfuel oil with said petroleum acid introduced therein to effectsuchcoagulation of said suspended or colloidal complexes as to permitsettling thereof, settling the coagulated complexes of hydrated lime andassociated carbonaceous material from said fuel oil, and drawing off thefuel oil thus clarified and substantially free from carbon and otherobjectionable solid materials.

it A method of producing fuel oil substantially free from carbon andother objectionable solid materials which comprises adding lime tohydrocarbon oil and subjecting such oil to cracking conditions to obtainvaporous products and unvaporized fuel oil containing suspended orcolloidal complexes of lime and associated carbonaceous material formedin the hydrocarbon oil under said cracking conditions, withdrawing saidfuel oil from said cracking conditions, introducing waste oil separablefrom the sulphuric acid sludge of petroleum refining intosa1d.

fuel oil, intimately contacting said suspended or colloidal complexes oflime and associated carbonaceous material contained in said fuel oilwith said waste oil introduced thereinto effect such coagulation of saidsuspended or colloidal complexes as to permit settling thereof, settlingthe coagulated complexes of hydrated lime and associated carbonaceousmaterial from said fuel oil, and drawing ofi the fuel oil thus clarifiedand substantially free from carbon and other objectionable solidmaterials.

15. A method of producing fuel oil substantiallyfree from carbon andother objectionablesolid materials which comprises adding lime tohydrocarbon oil and subjecting such oil to cracking conditions to obtainVaporous products and unvaporized'fuel oil containing suspended orcolloidal complexes of lime and associated carbonaceous material formedin the hydrocarbon oil under said cracking-conditions, withdrawing saidfuel oil from said cracking conditions, introducing an organic acidcontaining a naphthene ring, such as naphthenic acid, into said fueloil, intimately contacting said suspended or colloidal complexes of limeand associated carbonaceous material contained insaid fuel oil with saidorganic acid introduced therein to effect such coagulation of saidsuspended or collidal complexes as to permit settling thereof, settlingthe coagulated complexes of hydrated lime and associated carbonaceousmaterial from said fuel oil, and drawing ofi the fuel oil thus clarifiedand substantially free from carbon and other objectionable solidmaterials.

16. A method of producing fuel oil substantially free from carbon andother objece tionable solid materials which comprises adding lime tohydrocarbon 011 and sub ecting such oil to cracking conditions to obtainVaporous products and unvaporized fuel oil containing suspended orcolloidal complexes of lime and associated carbonaceous material formedin, the hydrocarbon oil undersaid cracking conditions, withdrawing saidfuel oil from said cracking conditions, dissolving a petroleum acidderived from the waste lyes of; petroleum refining in a petroleumsolvent,

such as gas oil, introducing such-solution of said acid into'said fueloil, intimately contact ing said suspended or colloidal complexes oflime and asso'ci'ated carbonaceous material contained in said fuel oiwith said acid in solution introduced therein to efiect such coagulationof said suspended or colloidal complexes as to permit settling thereof,settling the coagulated complexes of hydrated lime and associatedcarbonaceous material from said fuel oil, and drawing off the fuel oilthus clarified and substantially free from carbon and otherobjectionable solid materials.

17. A method of producing fuel oil substantially free from carbon andother objectionable solid materials which comprises adding lime tohyrocarbon oil and subjecting such oil to cracking conditions to obtainvaporous products and unvaporized fuel oil containing suspended orcolloidal complexes of lime and associated carbonaceous material formed1n the hydrocarbon 011 under sald sludge of petroleum refining with apetroleum.

distillate, such as gas oil, introducing such diluted waste oil intosaid fuel oil, intimately are v contactingsaid suspended or colloidalcomplexes of lime-and associated carbonaceous material contained in saidfuel oil with said dilutedwaste oil introduced therein to efi'eot suchcoagulation of said suspended or colloidal complexes as to permitsettling thereof, e

settling thecoagulated complexes of hydrated lime and associatedcarbonaceous material from said fuel oil, and drawing ofi the fuel oilthus clarified and substantially free from carbon and otherobjectionable solidomaterials. e,

.18. A method of producing fuel oil substantial'lyfree from carbonand'other objectionable solid materials which comprises adding lime tohydrocarbon oil and subjecting such. oil to cracking conditions toobtain Vaporous products and unvaporlzed fuel 011 containing suspendedor colloidal complexes of lime and associated carbonaceous materialformed in the hydrocarbon oil under said cracking conditions,withdrawing said fuel oil from said cracking conditions, dissolving anorganic acid containing a naphthenering, such as naphthenic acid, in apetroleum solvent, such as gas oil, introducing such solution of saidacid into said fuel oil intimately contacting said suspended orcolloidal complexes of lime and associated carbonaceous materialcontained in said fuel oil with said acid in solution introduced thereinto effect such coagulation of said suspended or colloidal complexes asto permit settling thereof, settling the coagulate'd complexes ofhydrated lime and associated carbonaceous material from said fuel oil,and drawing off the fuel oil thus clarified and substantially free fromcarbon 7 and other objectionable solid materials.

In testimony whereof I have afiixed my signature.

STEPHEN 'SWARTZ.

